CN112271281B - Composite cathode material, preparation method and application thereof, and lithium ion battery - Google Patents

Composite cathode material, preparation method and application thereof, and lithium ion battery Download PDF

Info

Publication number
CN112271281B
CN112271281B CN202011136753.7A CN202011136753A CN112271281B CN 112271281 B CN112271281 B CN 112271281B CN 202011136753 A CN202011136753 A CN 202011136753A CN 112271281 B CN112271281 B CN 112271281B
Authority
CN
China
Prior art keywords
layer
metal compound
positive electrode
lithium
cathode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011136753.7A
Other languages
Chinese (zh)
Other versions
CN112271281A (en
Inventor
贺理珀
陈巍
张耀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinwangda Power Technology Co ltd
Original Assignee
Sunwoda Electric Vehicle Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sunwoda Electric Vehicle Battery Co Ltd filed Critical Sunwoda Electric Vehicle Battery Co Ltd
Priority to CN202011136753.7A priority Critical patent/CN112271281B/en
Publication of CN112271281A publication Critical patent/CN112271281A/en
Application granted granted Critical
Publication of CN112271281B publication Critical patent/CN112271281B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application relates to a composite cathode material, a preparation method thereof and a lithium ion battery, and belongs to the technical field of batteries. A composite cathode material comprises a cathode material, a metal compound layer and a lithium peroxide layer, wherein the metal compound layer is coated on the surface of the cathode material, and the lithium peroxide layer is coated on the surface of the metal compound layer on the side away from the cathode material. The metal compound layer of the composite cathode material can be used as a catalyst to reduce the decomposition potential of lithium peroxide, and in the first charging process, the metal compound can catalyze the lithium peroxide to decompose efficiently and release Li + Carrying out high-efficiency lithium supplement; meanwhile, the metal compound layer is remained on the surface of the anode material, so that the metal compound layer can play a role of a physical barrier layer, the anode material is prevented from being in direct contact with the electrolyte, the occurrence of side reactions of the interface of the anode material is reduced, the stability of the anode material and the interface of the electrolyte can be improved, and the cycle performance of the battery is improved.

Description

Composite cathode material, preparation method and application thereof, and lithium ion battery
Technical Field
The invention relates to the technical field of batteries, in particular to a composite cathode material, a preparation method and application thereof and a lithium ion battery.
Background
Lithium ion batteries have the advantages of high energy density, good power performance, long cycle life, and the like, and have been widely used in the fields of consumer electronics, electric vehicles, energy storage, and the like. During the first charging process of the lithium ion battery, a passive film, namely an SEI film, composed of lithium salt is formed on the surface of the negative electrode, and the first irreversible capacity loss is caused. In order to improve the first effect and make up for the loss of active lithium caused by the formation of an SEI film of a negative electrode in the first charge-discharge process, a lithium supplement material is required to supplement lithium for the battery. However, the lithium replenishing efficiency of the traditional lithium replenishing material is low, and non-conductive inert substances can remain after lithium removal, so that the cycle performance of the battery is poor.
Disclosure of Invention
Accordingly, there is a need for a composite positive electrode material having high lithium replenishment efficiency and capable of improving battery cycle performance.
In addition, a preparation method and application of the composite cathode material and a lithium ion battery are also provided.
The composite cathode material comprises a cathode material, a metal compound layer and a lithium peroxide layer, wherein the metal compound layer is coated on the surface of the cathode material, and the lithium peroxide layer is coated on the surface of one side, far away from the cathode material, of the metal compound layer.
The metal compound layer of the composite cathode material can be used as a catalyst to reduce the decomposition potential of lithium peroxide, and in the first charging process, the metal compound can catalyze the lithium peroxide to decompose efficiently and release Li + Carrying out high-efficiency lithium supplement; meanwhile, the metal compound layer is remained on the surface of the anode material, so that the metal compound layer can play a role of a physical barrier layer, the anode material is prevented from being in direct contact with the electrolyte, the occurrence of side reactions of the interface of the anode material is reduced, the stability of the anode material and the interface of the electrolyte can be improved, and the cycle performance of the battery is improved.
In one embodiment, the metal compound layer is selected from at least one of a fluoride layer of Ni, a fluoride layer of Co, a fluoride layer of Mn, a fluoride layer of Fe, a fluoride layer of Cu, a sulfide layer of Ni, a sulfide layer of Co, a sulfide layer of Mn, a sulfide layer of Fe, and a sulfide layer of Cu.
In one embodiment, the positive electrode material is at least one selected from lithium cobaltate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, lithium manganate and nickel manganese binary material.
In one embodiment, the mass of the metal compound layer is 0.1% to 1% of the mass of the positive electrode material.
In one embodiment, the mass of the lithium peroxide layer is 1% to 4% of the mass of the positive electrode material.
In one embodiment, the ratio of the thickness of the metal compound layer to the thickness of the lithium peroxide layer is 1:2-3:2.
A preparation method of the composite cathode material comprises the following steps:
carrying out ball milling and mixing on the positive electrode material and the metal compound to obtain a coating;
and putting the coating into a lithium peroxide solution for evaporation crystallization to obtain the composite cathode material.
A lithium ion battery comprises the composite anode material or the composite anode material prepared by the preparation method of the composite anode material.
The composite anode material or the composite anode material prepared by the preparation method of the composite anode material is applied to the preparation of the lithium ion battery.
In one embodiment, the metal compound in the composite positive electrode material catalyzes the decomposition of the lithium peroxide at a charging voltage of 4V or more.
Drawings
Fig. 1 is a schematic structural view of a composite positive electrode material according to an embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A composite positive electrode material 10 comprises a positive electrode material 110 and a metal compound (M) x N y ) A layer 120 and a lithium peroxide layer 130, wherein the metal compound layer 120 is coated on the surface of the positive electrode material 110, and the lithium peroxide layer 130 is coated on the surface of the metal compound layer 120 far away from the positive electrode material 110.
The positive electrode material 110 is at least one selected from lithium cobaltate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, lithium manganate, and nickel manganese binary material.
Wherein the metal compound layer 120 can reduce both Li and Li 2 O 2 The decomposition potential plays a role in catalyzing the decomposition of the anode material, and simultaneously, the interface of the anode material 110 can be protected, and the long-term cycle performance is improved. If no catalyst is used, the decomposition voltage of the lithium peroxide is more than 4.5V, and the decomposition efficiency is less than 20%. Under the catalytic action of metal compound, the decomposition voltage is reduced to below 4V, and the decomposition efficiency is improved to nearly 100%.
Specifically, the metal compound layer 120 is selected from at least one of a fluoride layer of Ni, a fluoride layer of Co, a fluoride layer of Mn, a fluoride layer of Fe, a fluoride layer of Cu, a sulfide layer of Ni, a sulfide layer of Co, a sulfide layer of Mn, a sulfide layer of Fe, and a sulfide layer of Cu. Wherein, the metal fluoride layer can effectively catalyze the decomposition of the lithium peroxide and resist the corrosion of HF. The metal sulfide layer also has the function of a metal fluoride layer in the same way.
Further, the mass of the metal compound layer 120 is 0.1% to 1% of the mass of the positive electrode material 110. The mass of the metal compound layer 120 determines the thickness of the metal compound layer 120, and the proper thickness of the metal compound layer can effectively avoid the direct contact between the surface of the positive electrode material and the electrolyte, and reduce the occurrence of interface side reactions. However, the metal compound layer is an insulator for lithium ions and electrons, and the surface impedance of the material is increased due to the excessively thick coating layer, so that the power performance is influenced. Specifically, the thickness of the metal compound layer 120 is 20nm to 30nm.
Further, lithium peroxide (Li) 2 O 2 ) The mass of the layer 130 is 1% to 4% of the mass of the positive electrode material 110. The quality of the lithium peroxide layer 130 determines the thickness of the lithium peroxide layer, and if the thickness of the lithium peroxide layer is too small, the lithium replenishing capacity of the material is reduced, and if the thickness of the lithium peroxide layer is too large, the decomposition efficiency of the lithium peroxide is reduced, and the lithium replenishing efficiency is reduced. Specifically, the ratio of the thickness of the metal compound layer to the thickness of the lithium peroxide layer is 1:2 to 3:2. More specifically, the thickness of the lithium peroxide layer is 20nm to 40nm.
Wherein the particle size range of the composite positive electrode material is 2-35 mu m. The overlarge granularity can cause the lengthening of a lithium ion diffusion path, and influence the multiplying power and low-temperature performance of the battery; the excessively small particle size results in large specific surface area of the material, more serious interface side reaction, and influence on long-term cycle and gas production performance of the battery. Further, the composite positive electrode material has an average particle diameter of 15 μm or less.
The lithium supplement principle of the composite cathode material 10 is as follows:
Figure BDA0002736973430000041
in the metal compound M x N y Under catalysis of, li 2 O 2 Can efficiently decompose and release Li + And oxygen. The oxygen is removed by vacuumizing during secondary packaging of the battery, and the safety performance of the battery is not influenced.
The composite positive electrode material 10 has at least the following advantages:
1) The metal compound layer 120 of the composite cathode material 10 can be used as a catalyst to reduce the decomposition potential of lithium peroxide, and during the first charging process, the metal compound can catalyze the lithium peroxide to decompose efficiently and release Li + Carrying out high-efficiency lithium supplement; meanwhile, the metal compound layer 120 remains on the surface of the positive electrode material 10, and can play a role of a physical barrier layer, so that the positive electrode material 10 is prevented from being directly contacted with the electrolyte, the occurrence of side reactions at the interface of the positive electrode material 10 is reduced, the stability of the positive electrode material and the interface of the electrolyte can be improved, and the cycle performance of the battery is improved.
2) Li in the above composite positive electrode material 10 2 O 2 The surface of the composite anode material 10 generates a loose and porous appearance after decomposition, so that the electrolyte can be fully infiltrated conveniently, and the rate performance of the battery can be improved.
3) The composite anode material 10 has high lithium supplementing efficiency, and the lithium supplementing capacity can reach 1154mAh/g.
A preparation method of a composite cathode material is one of the preparation methods of the composite cathode material, and comprises the following steps:
step S210: and carrying out ball milling and mixing on the positive electrode material and the metal compound to obtain the coating.
The surface of the anode material after ball milling is coated with a layer of metal compound to form a metal compound layer, namely the coating is the anode material coated with the metal compound on the surface.
Further, in the step of ball milling and mixing the anode material and the metal compound, the rotation speed of the ball milling is 200rpm to 600rpm, and the ball milling time is 30min to 50min. Specifically, ball milling is performed using a ball mill. More specifically, the mass ratio of the ball milling beads to the positive electrode material in the ball mill is 10 to 20.
Wherein the particle size range of the positive electrode material is 1-34 μm. Specifically, the positive electrode material is at least one selected from lithium cobaltate, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, lithium manganate and a nickel-manganese binary material.
Wherein the particle size of the metal compound is 2 nm-20 nm. Specifically, the metal compound is at least one selected from the group consisting of a fluoride of Ni, a fluoride of Co, a fluoride of Mn, a fluoride of Fe, a fluoride of Cu, a sulfide of Ni, a sulfide of Co, a sulfide of Mn, a sulfide of Fe, and a sulfide of Cu. Further, the mass of the metal compound is 0.1% to 1% of the mass of the positive electrode material.
Step S220: and putting the coating into a lithium peroxide solution for evaporative crystallization to obtain the composite cathode material.
Wherein the mass of the solute in the lithium peroxide solution is 1-4% of the mass of the positive electrode material.
Wherein the solvent of the lithium peroxide solution is at least one selected from methanol, butanol, isopropanol and acetone.
Further, in the step of putting the coating into a lithium peroxide solution for evaporative crystallization, the temperature of the evaporative crystallization is 40-80 ℃.
Further, the step of putting the coating into a lithium peroxide solution for evaporative crystallization is specifically as follows: the coating is put into lithium peroxide solution and stirred at the stirring speed of 400 rpm-1000 rpm, and evaporation crystallization is carried out at the temperature of 40-80 ℃ until the solvent is completely volatilized.
Further, after the step of putting the coating into a lithium peroxide solution for evaporation crystallization, a drying step is also included.
Wherein, the coating is put into lithium peroxide solution for evaporation and crystallization to lead Li 2 O 2 The crystal is continuously precipitated and deposited on the surface of the metal compound to obtain the alloy with Li 2 O 2 And a metal compound double-coated anode material, namely a composite anode material.
Wherein the particle size range of the composite positive electrode material is 2-35 mu m. Further, the composite positive electrode material has an average particle diameter of 15 μm or less.
The preparation method of the composite cathode material is simple in process, is convenient for large-scale industrial production, and can accurately control the lithium supplement amount.
A lithium ion battery comprises the composite anode material or the composite anode material prepared by the preparation method of the composite anode material. The lithium ion battery has high initial efficiency and good cycle performance. The composite anode material or the composite anode material prepared by the preparation method of the composite anode material is applied to the preparation of the lithium ion battery. Further, the metal compound in the composite positive electrode material catalyzes the efficient decomposition of lithium peroxide at a charging voltage of 4V or more. Specifically, the charging rate was 0.33C.
The following are specific examples:
example 1
The preparation steps of the composite cathode material of the embodiment are as follows:
subjecting LiCoO to condensation 2 Positive electrode material and NiF 2 Simultaneously adding into a ball mill, and ball-milling at the rotating speed of 200rpm for 30min to obtain NiF 2 Coated LiCoO 2 A positive electrode material of which NiF 2 Accounts for LiCoO 2 Is 0.2wt%, ball milling beads and LiCoO 2 The mass ratio of (1) is 10.
Then, niF is added 2 Coated LiCoO 2 Positive electrode materialAddition of Li 2 O 2 Stirring the solution at a stirring speed of 400rpm at a temperature of 80 ℃ until the solvent is completely volatilized, and drying the solid at a temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And NiF 2 A double-coated composite positive electrode material, wherein Li 2 O 2 Account for LiCoO 2 Is 1wt%.
Example 2
The preparation steps of the composite cathode material of the embodiment are as follows:
mixing LiMn 2 O 4 Positive electrode material and CoF 2 Simultaneously adding the mixture into a ball mill, and ball-milling the mixture for 40min at the rotating speed of 400rpm to obtain CoF 2 Coated LiMn 2 O 4 Positive electrode material, wherein, coF 2 Occupied by LiMn 2 O 4 0.1wt%, ball milling beads and LiMn 2 O 4 The mass ratio of (1).
Then, the CoF is mixed 2 Coated LiMn 2 O 4 Material addition of Li 2 O 2 Stirring the solution at the temperature of 60 ℃ and the stirring speed of 500rpm until the solvent is completely volatilized, and drying the solid at the temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And CoF 2 A double-coated composite positive electrode material, wherein Li 2 O 2 Occupied by LiMn 2 O 4 Is 2wt%.
Example 3
The preparation steps of the composite cathode material of the embodiment are as follows:
mixing LiNi 0.9 Mn 0.1 O 2 Positive electrode material and MnF 2 Simultaneously adding the mixture into a ball mill, and ball-milling the mixture for 50min at the rotating speed of 300rpm to obtain MnF 2 Coated LiNi 0.9 Mn 0.1 O 2 A positive electrode material, wherein MnF 2 Account for LiNi 0.9 Mn 0.1 O 2 Is 0.5wt%, ball milling beads and LiNi 0.9 Mn 0.1 O 2 The mass ratio of (1) is 20.
Then, mnF 2 Coated LiNi 0.9 Mn 0.1 O 2 Materials plusLi incorporation 2 O 2 Stirring the solution at a stirring speed of 800rpm at a temperature of 80 ℃ until the solvent is completely volatilized, and drying the solid at a temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And MnF 2 A double-coated composite positive electrode material, wherein Li 2 O 2 Account for LiNi 0.9 Mn 0.1 O 2 Is 3wt%.
Example 4
The preparation steps of the composite cathode material of the embodiment are as follows:
reacting LiNi 0.33 Co 0.33 Mn 0.33 O 2 Cathode material and FeF 3 Simultaneously adding the mixture into a ball mill, and ball-milling for 40min at the rotating speed of 600rpm to obtain FeF 3 Coated LiNi 0.33 Co 0.33 Mn 0.33 O 2 Positive electrode material, of which FeF 3 Account for LiNi 0.33 Co 0.33 Mn 0.33 O 2 0.8wt%, ball milling beads and LiNi 0.33 Co 0.33 Mn 0.33 O 2 The mass ratio of (1) is 20.
Then, feF is reacted 3 Coated LiNi 0.33 Co 0.33 Mn 0.33 O 2 Adding Li into the positive electrode material 2 O 2 Stirring the solution at the temperature of 40 ℃ and the stirring speed of 1000rpm until the solvent is completely volatilized, and drying the solid at the temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And FeF 3 A double-coated composite positive electrode material, wherein Li 2 O 2 Account for LiNi 0.33 Co 0.33 Mn 0.33 O 2 Is 4wt%.
Example 5
The preparation steps of the composite cathode material of the embodiment are as follows:
reacting LiNi 0.5 Co 0.2 Mn 0.3 O 2 Adding the positive electrode material and CuS into a ball mill at the same time, and ball-milling at the rotating speed of 200rpm for 30min to obtain the CuS-coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 A positive electrode material, wherein CuS accounts for LiNi 0.5 Co 0.2 Mn 0.3 O 2 Is 0.2wt%, ball milling beads and LiNi 0.5 Co 0.2 Mn 0.3 O 2 The mass ratio of (1) is 10.
Then, cuS-coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 Material addition of Li 2 O 2 Stirring the solution at a temperature of 80 ℃ and a stirring speed of 400rpm until the solvent is completely volatilized, and drying the solid at a temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And a composite positive electrode material double-coated with CuS, wherein Li 2 O 2 Account for LiNi 0.5 Co 0.2 Mn 0.3 O 2 Is 1wt%.
Example 6
The preparation steps of the composite cathode material of the embodiment are as follows:
mixing LiNi 0.6 Co 0.2 Mn 0.2 O 2 Adding the positive electrode material and NiS into a ball mill at the same time, and ball-milling at the rotating speed of 500rpm for 40min to obtain NiS-coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 A positive electrode material, wherein NiS represents LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is 0.7wt%, ball milling beads and LiNi 0.6 Co 0.2 Mn 0.2 O 2 The mass ratio of (1) is 20.
Then, niS-coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Material addition of Li 2 O 2 Stirring the solution at the temperature of 40 ℃ and the stirring speed of 800rpm until the solvent is completely volatilized, and drying the solid at the temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And NiS double-coated composite anode material. Wherein Li 2 O 2 Account for LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is 2wt%.
Example 7
The preparation steps of the composite cathode material of the embodiment are as follows:
reacting LiNi 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and CoS was added simultaneously to the ball mill and ball milled at 400rpm for 40min to obtain a CoS-coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material, wherein CoS accounts for LiNi 0.8 Co 0.1 Mn 0.1 O 2 0.6wt%, ball milling beads and LiNi 0.8 Co 0.1 Mn 0.1 O 2 The mass ratio of (1) is 10.
Then, coS-coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 Material addition of Li 2 O 2 Stirring the solution at the temperature of 40 ℃ and the stirring speed of 1000rpm until the solvent is completely volatilized, and drying the solid at the temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 And CoS double-coated composite cathode material, wherein Li 2 O 2 Account for LiNi 0.8 Co 0.1 Mn 0.1 O 2 Is 2.5wt%.
Example 8
The preparation steps of the composite cathode material of the embodiment are as follows:
reacting LiNi 0.8 Co 0.15 Al 0.05 O 2 Adding the anode material and MnS into a ball mill at the same time, and ball-milling at the rotating speed of 300rpm for 30min to obtain MnS-coated LiNi 0.8 Co 0.15 Al 0.05 O 2 A positive electrode material, wherein MnS accounts for LiNi 0.8 Co 0.15 Al 0.05 O 2 Is 1wt%, ball milling beads and LiNi 0.8 Co 0.15 Al 0.05 O 2 The mass ratio of (1) is 20.
Then, mnS-coated LiNi 0.8 Co 0.15 Al 0.05 O 2 Material addition of Li 2 O 2 Stirring the solution at the temperature of 60 ℃ and the stirring speed of 200rpm until the solvent is completely volatilized, and drying the solid at the temperature of 120 ℃ for 12 hours to obtain the solid with Li 2 O 2 A composite positive electrode material double-coated with MnS, wherein Li 2 O 2 Account for LiNi 0.8 Co 0.15 Al 0.05 O 2 Is 2wt%.
Comparative example 1
Coating B in this comparative example 2 O 3 Of (4) a composite LiNi 0.6 Co 0.2 Mn 0.2 O 2 The preparation method of the cathode material comprises the following steps that the first charge capacity of the material can be improved by sintering and lithium supplement, and B 2 O 3 The coating can improve the first effect and the cycle performance.
(1) 200g of positive electrode material LiNi is taken 0.6 Co 0.2 Mn 0.2 O 2 Adding LiOH into the matrix M according to the Li/M =0.05%, uniformly mixing, heating the obtained mixture sample to 500 ℃ at the heating rate of 5 ℃/min under the air atmosphere, keeping the temperature for 1h, then heating to 700 ℃ and keeping the temperature for 5h, and finally naturally cooling. Sieving the sintered material with a 300-mesh sieve for later use;
(2) Firstly, 120g of the material in the step (1) is weighed, and H is added according to the boron element coating amount of 0.035% 3 BO 3 After the mixture is uniformly mixed, the mixture sample is heated to 300 ℃ at the heating rate of 5 ℃/min in the air atmosphere for sintering for 5h, and finally, the mixture is naturally cooled. Sieving with 360 mesh sieve to obtain coating B 2 O 3 Of (4) a composite LiNi 0.6 Co 0.2 Mn 0.2 O 2 A material.
Comparative example 2
Carbon-coated Li in this comparative example 2 NiO 2 The preparation steps of the lithium supplement material are as follows, and the lithium supplement material can be added during the preparation of the anode slurry, so that the purpose of lithium supplement is achieved.
(1) Mixing high purity Li 2 CO 3 (purity of>99.99 percent) is ball-milled and calcined in inert atmosphere, the calcining temperature is 800 ℃, and the high-purity product Li is obtained 2 O, purity of>99.9％；
(2) High purity Li from the above product 2 O and high-purity NiO with the molar ratio of Li 2 NiO =1.1 ball-milling in a nitrogen atmosphere at a speed of 350rpm for 10h, and then calcining in a nitrogen atmosphere at a calcination temperature of 650 ℃ for 4h to obtain Li 2 NiO 2 A material;
(3) Weighing appropriate amount of citric acid and adding Li 2 NiO 2 In the preparation method, ethanol is used as a solvent to carry out mechanical stirring and mixing, and ultrasonic dispersion is carried out for 1h to obtain a mixed solutionStirring the solution in water bath to volatilize the solvent;
(4) And (3) carrying out primary sintering on the dried product in a nitrogen atmosphere, wherein the sintering temperature is 350 ℃, and the time is 4h. Fully grinding the cooled Li and acetylene black, and then sintering the obtained product for the second time in an inert atmosphere at the sintering temperature of 650 ℃ for 9 hours to obtain the carbon-coated Li 2 NiO 2 And (5) supplementing lithium materials. Carbon-coated Li with carbon content 2 NiO 2 1% of the lithium-supplemented material.
Comparative example 3
The composite positive electrode material of the comparative example only coats the metal compound, and the preparation steps are as follows:
reacting LiNi 0.5 Co 0.2 Mn 0.3 O 2 Adding the positive electrode material and CuS into a ball mill at the same time, and ball-milling at the rotating speed of 200rpm for 30min to obtain the CuS-coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 A positive electrode material, wherein CuS represents LiNi 0.5 Co 0.2 Mn 0.3 O 2 Is 0.2wt%, ball milling beads and LiNi 0.5 Co 0.2 Mn 0.3 O 2 The mass ratio of (1) is 10.
The composite positive electrode materials prepared in examples 1 to 8 and different negative electrode materials were prepared into soft-package lithium ion batteries, which were named as S1 to S8. The cathodes of S1-S4 are graphite, the cathodes of S5-S8 are silicon and graphite composite materials, and the mass ratio of silicon to graphite is 1:4.
LiCoO, the pre-coated positive electrode material in examples 1 to 8 2 、LiMn 2 O 4 、LiNi 0.9 Mn 0.1 O 2 、LiNi 0.33 Co 0.33 Mn 0.33 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.8 Co 0.15 Al 0.05 O 2 The soft package lithium ion batteries prepared from the lithium ion batteries and different cathode materials are named as C1-C8.
The soft package lithium ion batteries of C1-C8 have the same formula and preparation process as those of the soft package lithium ion batteries of S1-S8 except for the anode material, namely, the soft package lithium ion batteries of C1 and the soft package lithium ion batteries of S1 have the same formula and preparation process except for the anode material; similarly, the formulas and preparation processes of C2 and S2, C3 and S3, C4 and S4, C5 and S5, C6 and S6, C7 and S7, and C8 and S8 are the same. Wherein, the cathodes of C1-C4 are graphite, the cathodes of C5-C8 are silicon and graphite composite materials, the mass ratio of silicon to graphite is 1:4,
the composite anode material prepared in the comparative example 1 and graphite are prepared into the lithium ion battery, and the lithium ion battery named as C9 and the lithium ion battery named as S6 have the same main components, formula and process except for the anode material coating substance.
Carbon-coated Li prepared in comparative example 2 2 NiO 2 The lithium supplement material is added into the positive electrode slurry of C1, the addition amount accounts for 1.2wt% of the mass of the positive electrode material, and then the lithium supplement material and graphite are prepared into a lithium ion battery named as C10. The formula and the process of the lithium ion battery of C10 are the same as those of the lithium ion battery of S1.
The CuS-only coated LiNi prepared in comparative example 3 0.5 Co 0.2 Mn 0.3 O 2 The anode material, the silicon and graphite composite material are prepared into the lithium ion battery named as C11. The formula and the process of the lithium ion battery of C11 are the same as those of the lithium ion battery of S5, and the mass ratio of silicon to graphite is 1:4.
The lithium ion batteries numbered S1 to S8 and C1 to C11 were subjected to a capacity test, a first coulombic efficiency test, and a capacity retention rate test at room temperature, and the results are shown in table 1.
The capacity testing process comprises the following steps: charging to 4.3V at room temperature under constant current of 1100mA, charging to current of less than 165mA at constant voltage of 4.3V, standing for 5min, and discharging to 2.8V under current of 1100mA to obtain discharge capacity.
First efficiency = first discharge capacity/(first charge capacity + formation capacity) × 100%.
The cycle test temperature is room temperature, the charge-discharge current is 3300mA, and the capacity retention rate at the 500 th cycle = 500 th cycle capacity/first cycle capacity × 100%.
TABLE 1
Figure BDA0002736973430000131
Figure BDA0002736973430000141
As can be seen from Table 1, comparing examples S1 to S8 with comparative examples C1 to C8, it can be seen that Li is coated 2 O 2 And the composite anode material of the metal compound has higher first-effect and cycle capacity retention rate. Especially for negative electrode materials containing silicon, li 2 O 2 And the double coating with the metal compound has more obvious effect on improving the first effect and the circulation of the battery.
Comparing C9 with S6, it can be seen that the lithium-supplemented coating layer of C9 exhibits higher first-pass and cycle capacity retention rates than other conventional coating materials.
Compared with S1 and C1, the C10 can be known to cause the cycle performance of the lithium ion battery to be reduced after the traditional lithium supplement additive is added, and the positive electrode material with the double coating layer has higher first effect and cycle capacity retention rate than the battery added with the traditional lithium supplement material.
As can be seen from comparison of C11 with C5 and S5, the coating of the metal compound only significantly improves the cycle performance, and the positive electrode material having the double coating layer exhibits higher first-pass and cycle capacity retention rates than the positive electrode material having only the metal compound coating layer.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. The composite cathode material is characterized by comprising a cathode material, a metal compound layer and a lithium peroxide layer, wherein the metal compound layer is coated on the surface of the cathode material, the lithium peroxide layer is coated on the surface of the metal compound layer far away from the cathode material, the metal compound layer is selected from at least one of a Ni fluoride layer, a Co fluoride layer, a Mn fluoride layer, an Fe fluoride layer, a Cu fluoride layer, a Ni sulfide layer, a Co sulfide layer, a Mn sulfide layer, an Fe sulfide layer and a Cu sulfide layer, the mass of the metal compound layer is 0.1-1% of that of the cathode material, and the mass of the lithium peroxide layer is 1-4% of that of the cathode material.
2. The composite positive electrode material according to claim 1, wherein the positive electrode material is selected from at least one of lithium cobaltate, a nickel cobalt manganese ternary material, a nickel cobalt aluminum ternary material, lithium manganate, and a nickel manganese binary material.
3. The composite positive electrode material according to claim 1, wherein a ratio of a thickness of the metal compound layer to a thickness of the lithium peroxide layer is 1 to 2.
4. A method for producing a composite positive electrode material according to any one of claims 1 to 3, characterized by comprising the steps of:
carrying out ball milling and mixing on the positive electrode material and the metal compound to obtain a coating;
and putting the coating into a lithium peroxide solution for evaporation crystallization to obtain the composite cathode material.
5. A lithium ion battery, characterized by comprising the composite cathode material of any one of claims 1~3 or the composite cathode material prepared by the preparation method of the composite cathode material of claim 4.
6. The use of the composite positive electrode material of any one of claims 1~3 or the composite positive electrode material produced by the method of claim 4 in the production of a lithium ion battery.
7. The use according to claim 6, wherein the metal compound in the composite positive electrode material catalyzes the decomposition of the lithium peroxide at a charging voltage of 4V or more.
CN202011136753.7A 2020-10-22 2020-10-22 Composite cathode material, preparation method and application thereof, and lithium ion battery Active CN112271281B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011136753.7A CN112271281B (en) 2020-10-22 2020-10-22 Composite cathode material, preparation method and application thereof, and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011136753.7A CN112271281B (en) 2020-10-22 2020-10-22 Composite cathode material, preparation method and application thereof, and lithium ion battery

Publications (2)

Publication Number Publication Date
CN112271281A CN112271281A (en) 2021-01-26
CN112271281B true CN112271281B (en) 2023-01-13

Family

ID=74342908

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011136753.7A Active CN112271281B (en) 2020-10-22 2020-10-22 Composite cathode material, preparation method and application thereof, and lithium ion battery

Country Status (1)

Country Link
CN (1) CN112271281B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114530634A (en) * 2020-11-23 2022-05-24 华为技术有限公司 Positive electrode lithium supplement agent and preparation method and application thereof
CN113036106A (en) * 2021-03-09 2021-06-25 昆山宝创新能源科技有限公司 Composite lithium supplement additive and preparation method and application thereof
CN113851654B (en) * 2021-09-22 2023-03-24 蜂巢能源科技有限公司 Cathode material for relieving oxygen release, and preparation method and application thereof
CN116666582A (en) * 2023-05-16 2023-08-29 广州凌顶能源科技有限公司 Metal oxide coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10224537B2 (en) * 2013-11-29 2019-03-05 Sila Nanotechnologies, Inc. Fluorides in nanoporous, electrically-conductive scaffolding matrix for metal and metal-ion batteries
WO2016126610A1 (en) * 2015-02-03 2016-08-11 Quantumscape Corporation Metal sulfide anolytes for electrochemical cells
KR20180028511A (en) * 2015-07-13 2018-03-16 실라 나노테크놀로지스 인코포레이티드 Stable lithium fluoride-based cathodes for metal and metal-ion batteries
US20170309914A1 (en) * 2016-04-20 2017-10-26 Ford Global Technologies, Llc Pre-lithiated lithium ion battery cell
KR20190095928A (en) * 2016-12-21 2019-08-16 로베르트 보쉬 게엠베하 Lithium Ion Battery and Manufacturing Method Thereof
CN108232131B (en) * 2017-12-06 2021-08-31 欣旺达电子股份有限公司 Metal fluoride coated ternary material and preparation method thereof
US11056679B2 (en) * 2018-07-31 2021-07-06 GRU Energy Lab Inc. Positive electrodes with active materials and temporary lithium additives for lithium ion electrochemical cells
CN113228346A (en) * 2018-12-21 2021-08-06 A123系统有限责任公司 Cathode with prelithiated coating, method for producing same and use thereof
CN111477840A (en) * 2019-01-24 2020-07-31 南京大学 Closed lithium ion battery anode based on oxyanion oxidation/reduction and preparation method thereof
CN110176641A (en) * 2019-06-03 2019-08-27 哈尔滨工业大学 A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry
CN111653758B (en) * 2020-06-12 2021-08-06 松山湖材料实验室 Composite lithium supplement agent and preparation method and application thereof

Also Published As

Publication number Publication date
CN112271281A (en) 2021-01-26

Similar Documents

Publication Publication Date Title
CN112271281B (en) Composite cathode material, preparation method and application thereof, and lithium ion battery
JP4063350B2 (en) Method for producing composite oxide using sol-gel method
CN108767216B (en) Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof
CN111082026A (en) Ternary cathode material coated with lithium tungstate and preparation method thereof
CN112164796B (en) Pre-lithiation additive for positive electrode material of lithium ion battery and preparation method and application thereof
CN111952547A (en) Surface-coated modified lithium ion battery positive electrode material and preparation method thereof
CN108134064B (en) Positive electrode material precursor, preparation method thereof and positive electrode material
CN110137464B (en) Lithium-rich nickel cobalt manganese oxide positive electrode material coated by vanadium lithium molybdate, positive electrode piece and preparation method thereof, and lithium battery
CN110416530B (en) Flower-like manganese dioxide/carbon composite material and preparation method and application thereof
CN112271279A (en) Composite cathode material, preparation method and application thereof, and lithium ion battery
KR20060008568A (en) Lithium-nickel complex oxide for cathode material of secondary batteries with non-aqueous electrolyte, a process for preparing the same and cathode material containing the same
CN115732674A (en) Sodium anode precursor material and preparation method and application thereof
CN113066988A (en) Negative pole piece and preparation method and application thereof
CN112038627A (en) Preparation method of TiN-coated nickel-cobalt-aluminum ternary positive electrode material
CN108807971B (en) Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof
CN115911324A (en) Positive electrode material, secondary battery, and electric device
CN114804235A (en) High-voltage nickel cobalt lithium manganate positive electrode material and preparation method and application thereof
CN114744188A (en) Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof
CN114927682A (en) LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material
CN114583151A (en) Activation method of lithium-rich manganese-based positive electrode material
CN113130900A (en) Vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof
CN113707870A (en) Cobalt-free cathode material and preparation method and application thereof
CN113113588A (en) Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy
CN112786825A (en) Positive electrode material and preparation method and application thereof
CN117254016B (en) High-ion mobility sodium-ion battery positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 518000 1-2 Floor, Building A, Xinwangda Industrial Park, No. 18 Tangjianan Road, Gongming Street, Guangming New District, Shenzhen City, Guangdong Province

Patentee after: Xinwangda Power Technology Co.,Ltd.

Address before: 518107 Xinwangda Industrial Park, No.18, Tangjia south, Gongming street, Guangming New District, Shenzhen City, Guangdong Province

Patentee before: SUNWODA ELECTRIC VEHICLE BATTERY Co.,Ltd.